CN110240692B - Bio-based flame-retardant furan epoxy resin and preparation method thereof - Google Patents

Bio-based flame-retardant furan epoxy resin and preparation method thereof Download PDF

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CN110240692B
CN110240692B CN201910539977.3A CN201910539977A CN110240692B CN 110240692 B CN110240692 B CN 110240692B CN 201910539977 A CN201910539977 A CN 201910539977A CN 110240692 B CN110240692 B CN 110240692B
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epoxy resin
furan
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retardant
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郭凯
孟晶晶
曾禹舜
方正
欧阳平凯
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Nanjing Tech University
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22Di-epoxy compounds
    • C08G59/26Di-epoxy compounds heterocyclic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50Amines
    • C08G59/504Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen

Abstract

The invention discloses a flame-retardant furan epoxy resin prepared from a furan epoxy resin monomer prepared based on hydroxymethylfurfural derivatization and a preparation method thereof, belonging to the technical field of high-molecular compounds. The preparation method specifically comprises the steps of uniformly mixing furan epoxy resin monomers with different structures with curing agents of different types in a hot melting way, carrying out injection molding, and then heating and curing to obtain the flame-retardant furan epoxy resin with excellent performance. The method directly adopts a body curing method, has simple operation process and shorter curing time, and the obtained bio-epoxy resin polymer material has excellent performance.

Description

Bio-based flame-retardant furan epoxy resin and preparation method thereof
Technical Field
The invention belongs to the technical field of high molecular compounds, and particularly relates to a bio-based flame-retardant furan epoxy resin and a preparation method thereof.
Background
The epoxy resin polymer is generally formed by cross-linking polymerization of an epoxy resin monomer material and a curing agent, and has wide application in the fields of coatings, adhesive adhesives, electronic and electrical industry, multi-component composite materials and engineering technology research. The epoxy resin polymer has the characteristics of high brittleness, flammability and the like, so that the application of the epoxy resin polymer in special industries is limited to a great extent. The traditional flame retardant material mainly solves the flame retardant problem by adding a specific auxiliary agent flame retardant, and the commonly used flame retardant mainly comprises a halogen combustion improver and a phosphorus-containing flame retardant. The halogen flame retardant material has low ultraviolet resistance stability, and easily generates a large amount of smoke and toxic gases at high temperature; phosphorus-containing flame retardant materials have poor heat resistance and compatibility, and often have dripping during combustion. Therefore, the requirements of flame retardance and environmental protection cannot be met.
2013, CN103435780A discloses a preparation method of phosphorus-bromine composite flame-retardant epoxy resin, which is characterized in that materials such as bisphenol A epoxy resin, tetrabromobisphenol A and a catalyst are subjected to reflux reaction for 4-5 hours to prepare a product liquid; and (3) distilling the obtained material under reduced pressure to remove the solvent, and continuously reacting the crude product for 3-4 hours at the temperature of 120-140 ℃ to obtain the phosphorus-bromine composite flame-retardant epoxy resin. The phosphorus-bromine composite flame-retardant epoxy resin has good flame-retardant effect and has the defect that toxic gas is easy to generate at high temperature. Due to the rapid development of furyl chemicals, patent CN108164689A in 2017 introduces a reactive phosphorus-containing flame retardant into the main chain of 2, 5-furandicarboxylic furan-based polyester to obtain the flame-retardant copolymerized furyl polyester, and the addition amount is small, the influence on the performance of the matrix polyester is small, and a relatively durable flame-retardant effect can be achieved.
Based on the development of bio-based functional materials, the research on all bio-based flame retardant materials is also initially promoted. 2017, patent CN108192078A discloses a full-bio-based flame-retardant epoxy resin, which is a full-bio-based epoxy resin product with flame-retardant property, and is prepared by introducing an epoxy group into an active group on gallic acid to obtain a bio-based epoxy monomer to replace bisphenol A epoxy resin DGEBA used in general industry, and mixing and curing the bio-based epoxy monomer with a bio-based curing agent difurfuryl amine with higher activity under certain conditions. The epoxy resin has the advantages of wide biological source, environmental protection, simple reaction process and good flame retardant property.
Since 2014, the preparation of bio-based furan epoxy resins has also progressed faster, but the research on the flame retardant performance of the bio-based furan epoxy resins as a whole is relatively less. Therefore, the preparation of the epoxy resin material with the flame retardant effect through the deep development of the renewable glycosyl furan compound has good research on the application value and is one of the hot directions of the research on the functionalization conversion application of the bio-based material.
Disclosure of Invention
The invention aims to provide a bio-based furan epoxy resin material with a flame retardant effect and a preparation method of the material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a bio-based flame-retardant furan epoxy resin, belongs to ABC type network polymer,
wherein A is A1 or A2,
wherein, the structural units A1, A2 and B, C are respectively:
Figure BDA0002101291580000021
wherein, the reticular structure has a repeating unit structure shown in formula I or formula II:
Figure BDA0002101291580000022
wherein m is 2 to 1000, n is 2 to 1000, o is 2 to 1000,
wherein R is shown as a formula III or a formula IV,
Figure BDA0002101291580000023
wherein the maximum heat release rate of the bio-based flame-retardant furan epoxy resin is 110W/g-230W/g measured by micro combustion calorimetry,
wherein said micro-combustion calorimetry is as determined by reference to: miao, J.T., et al (2017), "Biobased Heat Resistant Epoxy Resin with expression High BiomasssContent from2, 5-Furandicarboxylic Acid and Eugenol," ACS Sustainable chemistry & Engineering5 (8): 7003-7011.
The preparation method of the bio-based flame-retardant furan epoxy resin comprises the following steps:
(1) weighing a furan epoxy resin monomer, and introducing nitrogen to obtain a deoxyfuran epoxy resin monomer;
(2) adding a curing agent into the deoxyfuran epoxy resin monomer obtained in the step (1) in a nitrogen atmosphere, melting at high temperature, uniformly stirring, and pouring into a mold;
(3) and (3) placing the mold in the step (2) in a nitrogen atmosphere, curing at high temperature, cooling in the nitrogen atmosphere, and demolding to obtain the flame-retardant furan epoxy resin.
In the step (1), the furan epoxy resin monomer is prepared by taking bio-based hydroxymethyl furfural as a raw material. See, Jingzing Meng, Yushun Zeng, Guiqin Zhu, Jie Zhuang, Pengfei Chen, YaoCheng, Zheng Fang, Kai Guo, Polymer. chem., 2019, 10, 2370
In the step (1), the furan epoxy resin monomer is any one or two combinations of BOF and OmbFdE.
Figure BDA0002101291580000031
Wherein, the BOF and the OmbFdE are constructed by the following raw materials containing furan structures, wherein the raw materials have the structures shown in formulas V and VI, the nuclear magnetic spectrum of the raw materials is shown in figure 1 and figure 2,
Figure BDA0002101291580000032
in the step (2), the curing agent is an amine curing agent, preferably a diamine curing agent.
Wherein the amine curing agent is any one or the combination of two of 4,4 '-diamino diphenyl sulfone (44DDS) shown as a formula G and 3,3' -diamino diphenyl sulfone (33DDS) shown as a formula H to form NH in the epoxy resin2-R-NH2Structural unit
Figure BDA0002101291580000041
In the step (2), the addition amount of the curing agent is controlled, so that the molar ratio of ethylene oxide in the furan epoxy resin monomer to-NH in the curing agent is 1: 0.85-1: 1.2.
In the step (2), the high-temperature melting is carried out, wherein the temperature is 100-160 ℃, and preferably 110-150 ℃.
In the step (3), the curing temperature of the high-temperature curing is 160-240 ℃, wherein the preferred curing temperature is 170-190 ℃.
In the step (3), the curing time of the high-temperature curing is 3-10 hours, wherein 3-4 hours are preferred, and 3 hours are more preferred.
In the step (3), the curing is direct curing by a bulk method, and a catalyst and other auxiliary agents are not added in the curing process.
According to the invention, a bio-based furan epoxy monomer is used as a raw material, and a closed carbon layer structure is formed on the surface of the material by virtue of the characteristic that epoxy resin is partially decomposed at the initial stage of high temperature, so that the isolation of oxygen components is realized, and on the other hand, by virtue of the characteristic that diamine curing agents have high heat release in the decomposition process, the hot melting process of furan is accelerated, so that the carbon layer structure on the surface of the material is further tightened, and the oxygen isolation and heat propagation blocking are realized.
Has the advantages that: compared with the prior art, the invention has the following advantages:
(1) the environment-friendly non-petroleum-based epoxy resin material is prepared by simple conversion of the bio-based raw material hydroxymethyl furfural, the raw material is wide in source, the petroleum-based product can be replaced by the obtained product, the biological safety is high, the efficient utilization of biological resources is fully realized, and the development requirement of green chemistry is met.
(2) The epoxy resin material is simple to operate in the curing process, the process is convenient, and the greening level is high compared with halogen-containing flame-retardant materials.
(3) The invention realizes flame retardance by utilizing the self thermal decomposition characteristic of the raw materials, does not use halogen or phosphorus flame retardants or inorganic flame retardants, and has high biological safety.
(4) Compared with bisphenol A epoxy resin in the current market, the furan epoxy resin material prepared by the invention has the advantages that the maximum heat release rate is greatly reduced, and the flame retardant effect is greatly improved.
(5) The polymer material with good flame retardant property is prepared based on the synthesis of the bio-based hydroxymethylfurfural for the first time, so that the substitution of part of related petroleum-based chemicals can be met, and meanwhile, the foundation is laid for further realizing the functionalized research of the bio-based material.
Drawings
Of the BOF of FIG. 11H NMR spectrum.
FIG. 2 of OmbFdE1H NMR (a) and13c NMR (b) spectrum.
FIG. 3 is an infrared spectrum of a furan epoxy resin prepared with BOF/44DDS (example 1).
FIG. 4 is an infrared spectrum of a furan epoxy resin prepared with BOF/33DDS (example 3).
FIG. 5 is an infrared spectrum of furan epoxy resin prepared by OmbFdE/33DDS (example 4).
FIG. 6 DTG spectrum of BOF/44DDS prepared furan epoxy resin (example 1).
FIG. 7 DTG spectrum of BOF/33DDS prepared furan epoxy resin (example 3).
FIG. 8 flame retardant experiments for furan epoxy resins prepared with BOF/33DDS (a, example 3) and BOF/44DDS (b, example 1).
Detailed Description
The invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the description of the embodiments is only for illustrating the present invention and should not be taken as limiting the invention as detailed in the claims.
The micro-burn methods in the following examples are all references: miao, J.T., et al (2017), "Biobased Heat Resistant Epoxy Resin with expression High biological Content from2, 5-Furandicarboxylic Acid and Eugenol," ACS Sustainable Chemistry & Engineering5 (8): 7003-7011.
Example 1
Weighing furan epoxy resin BOF (2.4g, 10mmol) in a reaction bottle, introducing nitrogen, removing oxygen components, adding 4,4' -diamino diphenyl sulfone (44DDS, 1.2g, 5mmol) in the nitrogen atmosphere to further remove air, fully mixing and stirring, heating to 140 ℃ to melt the two, and mixing uniformly. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a nitrogen curing box at 185 ℃, curing for 3h, and naturally cooling in a nitrogen atmosphere to obtain a yellow transparent epoxy resin polymer (the crosslinking density is 2.38 mol/dm)3). Micro Combustion Calorimetry (MCC) experiments resulted in a maximum heat release rate of 175W/g (FIG. 8). The prepared bio-based flame-retardant furan epoxy resin has the following characteristic infrared absorption peaks: 681cm-1(δ,C-H,Ar),786cm-1(δ,C-H,Ar),1095cm-1(vs,C-O-C,ether),1200cm-1(vs,C-O-C,furan),1282cm-1(vas,C-O-C,ether),1354cm-1(vas,C-O-C,furan),1517-1598cm-1(δ,CH,furan),2855-2899cm-1(v,CH2),3384cm-1(v, OH) (FIG. 3) DTG of the prepared bio-based flame retardant furan epoxy resin is shown in FIG. 6.
Example 2
Weighing furan epoxy resin OmbFdE (3.5g, 10mmol) in a reaction bottle, introducing nitrogen, removing oxygen components, adding 4,4' -diamino diphenyl sulfone (44DDS, 1.2g, 5mmol) in the nitrogen atmosphere to further remove air, fully mixing and stirring, and heating to 130 ℃ to melt the two and uniformly mixing. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a nitrogen curing box at 175 ℃, curing for 4h, and naturally cooling in nitrogen atmosphere to obtain a yellow opaque epoxy resin polymer (the crosslinking density is 2.16 mol/dm)3). Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 223W/g.
Example 3
Weighing furan epoxy resin BOF (2.4g, 10mmol) in a reaction bottle, introducing nitrogen, removing oxygen components, adding 3,3' -diamino diphenyl sulfone (33DDS, 1.2g, 5mmol) in nitrogen atmosphere to further remove air, fully mixing and stirring, heating to 130 ℃ to melt the two, and mixing uniformly. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a nitrogen curing box at 170 ℃, curing for 3h, and naturally cooling in a nitrogen atmosphere to obtain a yellow transparent epoxy resin polymer (the crosslinking density is 3.62 mol/dm)3). Micro Combustion Calorimetry (MCC) experiments resulted in a maximum heat release rate of 112W/g (FIG. 8). The prepared bio-based flame-retardant furan epoxy resin has the following characteristic infrared absorption peaks: 690cm-1(δ,C-H,Ar),786cm-1(δ,C-H,Ar),1070cm-1(vs,C-O-C,ether),1208cm-1(vs,C-O-C,furan),1290cm-1(vas,C-O-C,ether),1363cm-1(vas,C-O-C,furan),1509-1598cm-1(δ,C-H,furan),2856-2880cm-1(v,CH2),3360cm-1(v, OH) (FIG. 4) DTG of the prepared bio-based flame retardant furan epoxy resin is shown in FIG. 7.
Example 4
Weighing furan epoxy resin OmbFdE (3.5g, 10mmol) in a reaction bottle, introducing nitrogen, removing oxygen components, adding 3,3' -diamino diphenyl sulfone (33DDS, 1.2g, 5mmol) in the nitrogen atmosphere to further remove air, fully mixing and stirring, and heating to 110 ℃ to melt the two and uniformly mixing. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a nitrogen curing box at 190 ℃, curing for 3h, and naturally cooling in a nitrogen atmosphere to obtain a dark yellow transparent epoxy resin polymer (the crosslinking density is 1.93 mol/dm)3). Micro Combustion Calorimetry (MCC) experiments gave a maximum heat release rate of 160W/g. The prepared bio-based flame-retardant furan epoxy resin has the following characteristic infrared absorption peaks: 681cm-1(δ,C-H,Ar),811cm-1(δ,C-H,Ar),1022cm-1(vs,C-O-C,ether),1208cm-1(vs,C-O-C,furan),1290cm-1(vas,C-O-C,ether),1387cm-1(vas,C-O-C,furan),1509-1598cm-1(δ,C-H,furan),2864-2962cm-1(v,CH2),3400cm-1(v, OH) (FIG. 5)
Example 5
Weighing furan epoxy resin OmbFdE (3.5g, 10mmol) in a reaction bottle, introducing nitrogen, removing oxygen components, adding 4,4' -diamino diphenyl sulfone (44DDS, 1.08g, 4.5mmol) in the nitrogen atmosphere to further remove air, fully mixing and stirring, heating to 135 ℃ to melt the two, and mixing uniformly. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a nitrogen curing box at 190 ℃, curing for 3h, and naturally cooling in a nitrogen atmosphere to obtain a dark yellow transparent epoxy resin polymer (the crosslinking density is 2.23 mol/dm)3). Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 178W/g.
Example 6
In a reaction flaskWeighing furan epoxy resin BOF (2.4g, 10mmol), introducing nitrogen, removing oxygen components, adding 4,4' -diamino diphenyl sulfone (44DDS, 1.32g, 5.5mmol) in nitrogen atmosphere to further remove air, mixing thoroughly, stirring, heating to 140 deg.C to melt the two and mixing uniformly. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a nitrogen curing box at 180 ℃, curing for 3h, and naturally cooling in a nitrogen atmosphere to obtain a yellow transparent epoxy resin polymer (the crosslinking density is 2.47 mol/dm)3). Micro Combustion Calorimetry (MCC) experiments gave a maximum heat release rate of 190W/g.
Comparative example 1
Weighing bisphenol A epoxy resin (3.4g, 10mmol) in a reaction bottle, introducing nitrogen, removing oxygen components, adding 4,4' -diamino diphenyl sulfone (44DDS, 1.2g, 5mmol) in nitrogen atmosphere to further remove air, mixing thoroughly, heating to 150 deg.C to melt the two and mixing uniformly. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a 235 ℃ nitrogen curing box, curing for 3h, and naturally cooling in a nitrogen atmosphere to obtain a dark yellow transparent epoxy resin polymer (the crosslinking density is 1.18 mol/dm)3). Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 499W/g.
Comparative example 2
Weighing bisphenol A epoxy resin (3.4g, 10mmol) in a reaction bottle, introducing nitrogen, removing oxygen components, adding 3,3' -diamino diphenyl sulfone (33DDS, 1.2g, 5mmol) in nitrogen atmosphere to further remove air, fully mixing and stirring, heating to 150 ℃ to melt the bisphenol A epoxy resin and the nitrogen, and mixing uniformly. Uniformly pouring the materials into a stainless steel mould plate, moving the mould plate into a nitrogen curing box at 215 ℃, curing for 3h, and naturally cooling in a nitrogen atmosphere to obtain a dark yellow transparent epoxy resin polymer (the crosslinking density is 1.46 mol/dm)3). Micro Combustion Calorimetry (MCC) test results in a maximum heat release rate of 553W/g.
Comparing the results of the Micro Combustion Calorimetry (MCC) experiments on furan epoxy resins (examples 1-6) and petroleum-based bisphenol a epoxy resins (comparative examples 1-2), it can be found that, compared with the most commonly used bisphenol epoxy resin materials in the current market, the furan bio-based epoxy resin polymer material has a significantly lower maximum heat release rate and a very good flame retardant property.

Claims (6)

1. A bio-based flame-retardant furan epoxy resin is characterized in that the bio-based flame-retardant furan epoxy resin is a reticular polymer consisting of A, B, C three monomers,
wherein A is A1 or A2,
wherein, the structural units A1, A2 and B, C are respectively:
Figure FDA0002414190310000011
wherein, the reticular structure has a repeating unit structure shown in a formula I or a formula II:
Figure FDA0002414190310000012
wherein m is 2 to 1000, n is 2 to 1000, o is 2 to 1000,
wherein R is shown as a formula III or a formula IV,
Figure FDA0002414190310000013
2. the method of preparing a bio-based flame retardant furan epoxy resin of claim 1, comprising the steps of:
(1) weighing a furan epoxy resin monomer, and introducing nitrogen to obtain a deoxyfuran epoxy resin monomer;
(2) adding a curing agent into the deoxyfuran epoxy resin monomer obtained in the step (1) in a nitrogen atmosphere, melting at high temperature, uniformly stirring, and pouring into a mold;
(3) placing the mold in the step (2) in a nitrogen atmosphere, curing at high temperature, cooling in the nitrogen atmosphere, and demolding to obtain the flame-retardant furan epoxy resin;
in the step (1), the furan epoxy resin monomer is any one or two combinations of BOF and OmbFdE,
Figure FDA0002414190310000021
in the step (2), the amine curing agent is any one or the combination of two of 4,4 '-diaminodiphenyl sulfone shown in a formula G and 3,3' -diaminodiphenyl sulfone shown in a formula H,
Figure FDA0002414190310000022
in the step (2), the addition amount of the curing agent is controlled, so that the molar ratio of ethylene oxide in the furan epoxy resin monomer to-NH in the curing agent is 1: 0.85-1: 1.2.
3. The method for preparing bio-based flame retardant furan epoxy resin according to claim 2, wherein in the step (1), the furan epoxy resin monomer is prepared from bio-based hydroxymethylfurfural.
4. The method for preparing bio-based flame retardant furan epoxy resin according to claim 2, wherein in the step (2), the high temperature melting is performed at a temperature of 100-160 ℃.
5. The method for preparing bio-based flame retardant furan epoxy resin according to claim 2, wherein in the step (3), the curing temperature is 160-240 ℃ when the curing is carried out at high temperature.
6. The method for preparing bio-based flame retardant furan epoxy resin according to claim 2, wherein in the step (3), the curing time is 3-10 h due to the high-temperature curing.
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